Glycidyl esters of alpha, alpha branched acids from renewable sources and formulations thereof

Abstract

The invention relates to compositions of α,α-branched alkane carboxylic acids glycidyl esters which derived from rosin and or hydrogenated rosin reacted with an epihalohydrin. The above glycidyl esters compositions can be used for example, as monomer in binder compositions for paints or adhesives, as reactive diluent or as acid scavenger. This invention is also about the uses of rosin and or hydrogenated rosin glycidyl ester in combinations with polyester polyols, or acrylic polyols, or polyether polyols.

1 . A process for the manufacture of glycidyl esters of rosin and/or hydrogenated rosin, comprising
 (a) reacting a rosin acid with a epoxyalkyl halide in a 1.01-20 molar excess, in the presence of water and a water-miscible solvent, and in the presence of a catalyst, in an amount of at most 45 mol % of the molar amount of the rosin acid, at a temperature in the range of from 30 to 110° C. during a period of time in the range of from 0.5 to 2.5 hr,   (b) adding an alkali metal hydroxide or alkali metal alkanolate up to a molar ratio in the range of from 0.9:1 to 1.2:1 as to the rosin acid and reacting at a temperature of from 0 to 80° C. to prepare a reaction mixture,   (c) distilling the reaction mixture to remove the excess epoxyalkyl halide solvent and water formed, and   (d) removing an alkali metal halide salt by washing the obtained glycidyl ester with water.   
     
     
         2 . The process of  claim 1  in which the amount of epoxyalkyl halide is reacted in a coupling reaction with the rosin acid, in the molar ratio of epoxyalkyl halide to acid that is in the range of from 1.02:1 to 1.50:1, to form an intermediate reaction product comprising a halohydrin, wherein
 the epoxyalkyl halide is added to the acid with appropriate cooling of the reaction mixture to keep the temperature of the reaction mixture below 80° C., whereupon the epoxyalkyl halide and the acid are reacted at a temperature below 80° C. for a time sufficient to fully convert the amount of acid, and wherein the process further comprises the steps of 
 optionally removing any unreacted epoxyalkyl halide prior to the ring closure reaction, 
 subjecting the reaction product to a ring closure reaction (DHC) and optionally to one or more after treatments (ADHC) for removal of any remaining halo functionality, 
 optionally adding a solvent before or after the DHC to reduce the viscosity and to promote the phase separation after the water washing to remove the salt, and 
 optionally using a reduced reactor pressure and reflux excess of the epoxyalkyl halide back into the reactor for temperature control. 
 
     
     
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         19 . A resin formulation comprising the glycidyl ester of rosin and/or hydrogenated rosin produced by the process of  claim 1  and a resin, wherein in the resin is selected from the group consisting of a polyester polyol resin, an acrylic polyol resin, a polyether polyol resin, a polyether-ester polyol resin, an epoxy resin and combinations thereof. 
     
     
         20 . The resin formulation of  claim 19  wherein the resin is a polyester polyol resin obtained by the reaction of a polycarboxylic acid compound and a mixture of rosin and/or hydrogenated rosin glycidyl esters, wherein the polycarboxylic acid compound is obtained by reacting of one or more multifunctional polyol with one or more anhydride or acid anhydrides. 
     
     
         21 . The resin formulation of  claim 20  wherein the acid value of the polyester polyol is lower than 20 mg KOH/g. 
     
     
         22 . The resin formulation of  claim 20  having a number average molecular weight (Mn) between 300 and 7000 Dalton, and a hydroxyl value between 40 and 320 mg KOH/g. 
     
     
         23 . The resin formulation of  claim 19  wherein the resin is an acrylic polyol resin obtained reacting an epoxy group with a carboxylic acid group of an ethylene carboxylic acid compounds from an hydroxyl ethylene carboxylate ester monomers, which are reacted with one or more unsaturated monomers via a radical polymerization reaction. 
     
     
         24 . The resin formulation of  claim 23  having a hydroxyl value between 50 and 180 mgKOH/g and a number average molecular weight (Mn) between 1500 and 50000 Dalton. 
     
     
         25 . The resin formulation of  claim 23  prepared in the presence of a polyester polyol 
     
     
         26 . A clear coating composition comprising 10 to 40 weight % of an aliphatic isocyanate, 0-25 weight % of the polyester polyol of  claim 20 , and 40 to 70 weight % the acrylic polyol of  claim 23 , with all weight % based on solids after evaporation of the solvent. 
     
     
         27 . The resin formulation of  claim 19  wherein the resin is a polyether polyol resin obtained by the reaction of at least one polyol having at least three hydroxyl groups and a mixture of rosin and/or hydrogenated rosin glycidyl esters. 
     
     
         28 . The resin formulation of  claim 27  having a number average molecular weight (Mn) is lower than 4500 Dalton and the hydroxyl value is above 120 mg KOH/g solids on solid.